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Publication numberUS4764599 A
Publication typeGrant
Application numberUS 06/913,376
Publication dateAug 16, 1988
Filing dateSep 30, 1986
Priority dateOct 10, 1985
Fee statusLapsed
Also published asDE3536196A1, EP0218206A2, EP0218206A3, EP0218206B1
Publication number06913376, 913376, US 4764599 A, US 4764599A, US-A-4764599, US4764599 A, US4764599A
InventorsHorst Colberg, Erwin Hahn
Original AssigneeBasf Aktiengesellschaft
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Disazo compounds containing an N,N-bis(2-amino-benzoyl)piperazine derivative as the diazo component
US 4764599 A
Abstract
Sulfo-free compounds of the formula ##STR1## where R is hydrogen or C1 -C4 -alkyl and
K1 and K2 independently of one another are a radical of a coupling component, and the rings A and B may furthermore be monosubstituted or polysubstituted by fluorine, chlorine, bromine, nitro, methyl, trifluoromethyl, ethyl, acetyl, benzoyl, a carboxylic ester group, unsubstituted or substituted carbamyl or sulfamyl, an aryl sulfonate group, C1 -C4 -alkylsulfonyl, unsubstituted or substituted phenylsulfonyl, cyano or acylamino or a fused ring, are very useful as pigments for coloring printing inks, surface coatings or plastics.
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Claims(3)
We claim:
1. A sulfo-free compound of the formula ##STR159## where R is hydrogen or C1 -C4 -alkyl and
K1 and K2 independently of one another are a radical of a coupling component, and the rings A and B are unsubstituted, or are monosubstituted or polysubstituted by fluorine, chlorine, bromine, nitro, methyl, trifluoromethyl, ethyl, acetyl, benzoyl, COOCH3, COOC2 H5, COOC3 H7, COOCH(CH3)2, COOC4 H9, COOC6 H5, COOC6 H13, COOC8 H17, COOC2 H4 OCH3, COOC2 H4 OC2 H5, COOCH2 C6 H5, CONH2, CONHCH3, CONHC2 H5, CONHC3 H7, CONHC4 H9, CONHCH(CH3)2, CONHCH2 C6 H5, CONHC6 H5, CONHC6 H4 Cl, CONHC6 H3 Cl2, CONHC6 H2 Cl3, CONHC6 H4 Br, CONHC6 HL4 OCH3, CONHC6 H4 CH3, CONHC6 H4 OC2 H5, CONHC6 H3 Cl(OCH3), CONHC6 H4 NHCOCH.sub. 3, CONHC6 H4 NHCOC6 H5, CONHNHCOC6 H5, CONHNHCOC6 H4 Cl, CONHNHCOC6 H4 CH3, SO2 NH2, SO2 NHCH3, SO2 NHC2 H5, SO2 NHC3 H7, SO2 NHC4 H9, SO2 NHCH(CH3)2, SO2 NHCH2 C6 H5, SO2 NHC6 H5, SO2 NHC6 H4 Cl, SO2 NHC6 H3 Cl2, SO2 NHC6 H2 Cl3, SO2 NHC6 H4 Br, SO2 NHC6 H4 OCH3, SO2 NHC6 H4 CH3, SO2 NHC6 H4 OC2 H5, SO2 NHC6 H3 Cl(OCH3), SO2 NHC6 H4 NHCOCH3, SO2 NHC6 H4 NHCOC6 H5, SO2 NHNHCOC6 H5, SO2 NHNHCOC6 H4 Cl, SO2 NHNHCOC6 H4 CH3, SO2 OC6 H5, SO2 OC6 H4 CH3, SO2 OC6 H4 Cl, SO2 OC6 H4 Br, SO2 OC6 H4 OCH3, SO2 OC.sub. 6 H4 NHCOCH3, SO2 OC6 H3 Cl2, SO2 C6 H5, SO2 C6 H4 Cl, NHCOCH3, NHCOC2 H5, NHCOC6 H5, NHCONH2, NHCON(CH3)2, NHCONHC6 H5, C1 -C4 -alkylsulfonyl or cyano.
2. A compound as claimed in claim 1 of the formula ##STR160## where K3 and K4 independently of one another are each a radical of the formulae ##STR161## where R1 is C1 -C4 -alkoxy, phenoxy which is unsubstituted or is substituted by chlorine, or arylamino which is unsubstituted or is substituted by chlorine, bromine, methyl, methoxy, ethoxy, nitro, cyano, acetamino, carbamyl, or sulfamyl;
R2 is aryl which is unsubstituted or is substituted by chlorine, bromine, methyl, methoxy, ethoxy, nitro, cyano, acetamino, carbamyl, or sulfamyl;
R3 is hydrogen, methyl, carboxyl, C1 -C8 -alkoxycarbonyl, carbamyl or the substituents stated for R2 ;
R4 is hydrogen or the substituents stated for R2,
R5 is hydrogen or C1 -C13 -alkyl;
R6 is hydrogen, hydroxyl, amino or C1 -C4 -alkyl;
R7 is hydrogen, cyano, carbamyl, acetyl or benzoyl;
R8 and R13 independently of one another are each hydrogen, C1 -C22 alkyl which is unsubstituted or substituted by hydroxy, methoxy, cyano, carbomethoxy, carboethoxy, acetoxy, ethoxycarbonyl, acetylamino, phenoxycarbonyloxy, phenylaminocarbonyloxy, butylaminocarbonyloxy, phenyl, or sulfo; phenyl or benzyl;
R9, R10 and R11 independently of one another are each hydrogen or C1 -C8 alkyl which is unsubstituted, or C2 -C6 -alkyl which is substituted by hydroxyl, cyano, alkoxy of 1 to 8 carbon atoms, phenoxy, phenoxyethoxy or benzyloxy; cyclohexyl, or phenyl, or R10 and R11 together with the nitrogen form a 5-membered or 6-membered heterocyclic ring;
R12 and R17 independently of one another are each oxygen, iminio or cyanoimino;
R14 is a radical R8, amino, C1 -C8 alkanoylamino, or benzoylamino which is unsubstituted or is monosubstituted or disubstituted by hydroxyl, chlorine, methyl, methoxy, acetylamino, nitro or amino;
R15 is hydrogen or phenyl which is unsubstituted or is monosubstituted, disubstituted or trisubstituted by chloro, bromo, methoxy or methyl;
R16 is hydroxyl, methyl, a carboxylic C1 -C2 -alkyl ester group, a member selected from the group consisting of NHCOCH3, NHCOC2 H5, NHCOC3 H7, NHCOC6 H5, NHCOC6 H4 Cl, NHCOC6 H3 Cl2, NHCOC6 H4 Br, NHCOC6 H4 OCH3, NHCONH2, NHCONHC6 H5 and NHCOCONHC6 H5 ; or a radical R15,
and the ring A is unsubstituted or is substituted in the stated manner and the phenylene radicals A are unsubstituted or are monosubstituted or polysubstituted by chlorine, bromine or nitro, the substituents being identical or different in the case of polysubstitution.
3. A compound as claimed in claim 2, wherein
R1 is NHC6 H5 which is unsubstituted or is monosubstituted or polysubstituted by chlorine, bromine, methyl, methoxy, ethoxy, nitro, cyano, acetamino, carbamyl or sulfamyl, the substituents being identical or different in the case of polysubstitution;
R2 is phenyl which is unsubstituted or is monosubstituted or polysubstituted by chlorine, bromine, methyl, methoxy, ethoxy, nitro, cyano, acetamino, carbamyl or sulfamyl, the substituents being identical or different in the case of polysubstitution;
R3 is hydrogen, methyl, C1 -C4 -alkoxycarbonyl, carbamyl, C1 -C4 -alkylaminocarbonyl or the radicals given for R2 ;
R4 is hydrogen or the radicals given for R2 ;
R5 is hydrogen or C1 -C8 -alkyl;
R6 is hydrogen, cyano, carbamyl, acetyl or benzoyl;
R8 and R13 independently of one another are each hydrogen, C1 -C22 alkyl, benzyl or a radical R2 ;
R9, R10 and R11 independently of one another are each hydrogen, C1 -C8 alkyl, cyclohexyl, benzyl or a radical R2, or R10 and R11 together with the nitrogen form a 5-membered or 6-membered heterocyclic ring;
R12 and R17 independently of one another are each oxygen, imino or cyanoimino;
R14 is a radical R8 or C1 -C8 alkanoylamino or benzoylamino which is unsubstituted or is substituted by hydroxyl, chlorine, methyl, methoxy, acetylamino, nitro or amino;
R15 is hydrogen or a radical R2 and R16 is methyl or a radical R2.
Description

The present invention relates to sulfo-free compounds of the general formula I ##STR2## where

R is hydrogen or C1 -C4 -alkyl and

K1 and K2 independently of one another are a radical of a coupling component, and the rings A and B may furthermore be monosubstituted or polysubstituted by fluorine, chlorine, bromine, nitro, methyl, trifluoromethyl, ethyl, acetyl, benzoyl, a carboxylic ester group, unsubstituted or substituted carbamyl or sulfamyl, an aryl sulfonate group, C1 -C4 -alkylsulfonyl, unsubstituted or substituted phenylsulfonyl, cyano or acylamino or a fused ring.

Specific examples of substituents for rings A and B, in addition to those stated above are COOCH3, COOC2 H5, COOC3 H7, COOCH(CH3)2, COOC4 H9, COOC6 H5, COOC6 H13, COOC8 H17, COOC2 H4 OCH3, COOC2 H4 OC2 H5, COOCH2 C6 H5, CONH2, CONHCH3, CONHC2 H5, CONHC3 H7, CONHC4 H9, CONHCH(CH3)2, CONHCH2 C6 H5, CONHC6 H5, CONHC6 H4 Cl, CONHC6 H3 Cl2, CONHC6 H2 Cl3, CONHC6 H4 Br, CONHC6 H4 OCH3, CONHC6 H4 CH3, CONHC6 H4 OC2 H5, CONHC6 H3 Cl(OCH3), CONHC6 H4 NHCOCH3, CONHC6 H4 NHCOC6 H5, CONHNHCOC6 H5, CONHNHCOC6 H4 Cl, CONHNHCOC6 H4 CH3, SO2 NH2, SO2 NHCH3, SO2 NHC2 H5, SO2 NHC3 H7, SO2 NHC4 H9, SO2 NHCH(CH3)2, SO2 NHCH2 C6 H5, SO2 NHC6 H5, SO2 NHC6 H4 Cl, SO2 NHC6 H3 Cl2, SO2 NHC6 H2 Cl3, SO2 NHC6 H4 Br, SO2 NHC6 H4 OCH3, SO2 NHC6 H4 CH3, SO2 NHC6 H4 OC2 H5, SO2 NHC6 H3 Cl(OCH3), SO2 NHC6 H4 NHCOCH3, SO2 NHC6 H4 NHCOC6 H5, SO2 NHNHCOC6 H5, SO2 NHNHCOC6 H4 Cl, SO2 NHNHCOC6 H4 CH3, SO2 OC6 H5, SO2 OC6 H4 CH3, SO2 OC6 H4 Cl, SO2 OC6 H4 Br, SO2 OC6 H4 OCH3, SO2 OC6 H4 NHCOCH3, SO2 OC6 H3 Cl2, SO2 CH3, SO2 C2 H5, SO2 C6 H5, SO2 C6 H4 Cl, NHCOCH3, NHCOC2 H5, NHCOC6 H5, NHCONH2, NHCON(CH3)2 and NHCONHC6 H5.

Examples of suitable coupling components K1 H and K2 H are compounds of the phenol, naphthol, acetoacetarylide, pyrazolone, quinolone, pyridine, pyrimidine, isoquinoline and pyrazolo[5,1-b]quinazolone series. Apart from phenol, o-, m- and p-cresol, 1-naphthol, 2-naphthol and resorcinol, these compounds are essentially of the formulae: ##STR3## where R1 is C1 -C4 -alkoxy, unsubstituted or substituted phenoxy or unsubstituted or substituted arylamino,

R2 is unsubstituted or substituted aryl,

R3 is hydrogen, methyl, carboxyl, C1 -C8 -alkoxycarbonyl, unsubstituted or substituted carbamyl or the substituents stated for R2,

R4 is hydrogen or the substituents stated for R2,

R5 is hydrogen or C1 -C13 -alkyl,

R6 is hydrogen, hydroxyl, unsubstituted or substituted amino or C1 -C4 -alkyl,

R7 is hydrogen, cyano, carbamyl, acetyl or benzoyl,

R8 and R13 independently of one another are each hydrogen or unsubstituted or substituted alkyl, cycloalkyl, phenyl or benzyl,

R9, R10 and R11 independently of one another are each hydrogen or unsubstituted or substituted alkyl, cycloalkyl or phenyl, or R10 and R11 together with the nitrogen may furthermore form a 5-membered or 6-membered heterocyclic ring,

R12 and R17 independently of one another are each oxygen, amino or cyanoimino,

R14 is a radical R8, amino or acylamino,

R15 is hydrogen or unsubstituted or substituted phenyl and

R16 is hydroxyl, methyl, a carboxylic ester group or unsubstituted or substituted aryl or acylamino, and the ring A may be substituted in the stated manner.

Specific examples of the radicals R1 to R16, in addition to those listed above are the following substituents:

R1 is OCH3, OC2 H5, OC6 H5, OC6 H4 Cl, OC6 H3 Cl2, NHC6 H5, NHC6 H4 Cl, NHC6 H3 Cl2, NHC6 H2 Cl3, NHC6 H3 Cl(CH3), NHC6 H4 CH3, NHC6 H4 C2 H5, NHC6 H3 (OCH3)2, NHC6 H3 (CH3)(OCH3), NHC6 H3 (CH3)2, NHC6 H2 (OCH3)2 Cl, NHC6 H2 (OCH3)(CH3)Cl, NHC6 H3 Cl(OCH3), NHC6 H4 NHCOCH3, NHC6 H4 NHCOC6 H5, NHC6 H4 OC2 H5, ##STR4## or NHC6 H3 (OC2 H5)2 ; R2 is C6 H5, C6 H4 Cl, C6 H4 CH3, C6 H4 OCH3, C6 H4 OC2 H5, C6 H4 NHCOCH3, C6 H4 NHCOC6 H5, C6 H3 Cl2, C6 H3 (CH3)2, C6 H3 (OCH3)2, C6 H3 (OC2 H5)2, C6 H3 Cl(CH3), C6 H3 Cl(OCH3), C6 H3 (CH3)(OCH3), C6 H2 Cl3, C6 H2 (OCH3)2 Cl, C6 H2 (OCH3)Cl(CH3), ##STR5## C6 H4 NO2, C6 H4 COCH3 or C6 H4 COC6 H5 ;

R3 is COOCH3, COOC2 H5, COOC3 H7, COOC4 H9, CONH2, CONHCH3, CONHC2 H5, CONHC3 H7 or CONHC4 H9 ;

R5 is CH3, C2 H5, C3 H7, C4 H9, C6 H13, C8 H17, C12 H25 or C13 H27 ;

R6 is CH3, C2 H5, C3 H7, C4 H9, C5 H11 α-ethylphenyl, phenyl, methylphenyl or chlorophenyl;

R8 and R13 are each methyl, ethyl, propyl, butyl, β-hydroxyethyl, β-methoxyethyl, γ-methoxypropyl, β-cyanoethyl, β-carbomethoxyethyl, β-carboethoxyethyl, β-acetoxyethyl, β-ethoxycarbonylethyl, γ-acetylaminopropyl, phenoxycarbonyloxyethyl, phenylaminocarbonyloxyethyl, butylaminocarbonyloxyethyl, benzyl, β-phenethyl, phenyl, dichlorophenyl, trichlorophenyl, acetylaminophenyl, carboxyphenyl, cyanophenyl, chlorophenyl, sulfoethyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, tridecyl, methylphenyl, dimethylphenyl, methylchlorophenyl, methoxyphenyl, heptyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, oleyl or other radicals of industrial fatty amines, such as coconut fatty amine or tallow fatty amine or their hydrogenation products; other examples are amino-substituted alkyl radicals, such as C1 -C18 -mono- or dialkylamino-substituted alkyl, cycloalkylaminoalkyl, aralkylaminoalkyl, or alkyl substituted by a N-heterocylic structure, and these aminoalkyl radicals may furthermore be quaternary radicals. Alkyl is preferably of 2 or 3 carbon atoms, ie. of the formula c2 H4 or, in particular, C3 H6. Specific examples of radicals are ##STR6## R9, R10 and R11 are each alkyl of 1 to 8 carbon atoms, C2 -C6 -alkyl which is substituted by hydroxyl, cyano, alkoxy of 1 to 8 carbon atoms, phenoxy, phenoxyethoxy or benzyloxy, or cyclohexyl, benzyl, phenylethyl, phenylhydroxyethyl, phenylpropyl or phenylbutyl, or phenyl which is unsubstituted or substituted by chlorine, methyl, methoxy or ethoxy, or polyalkoxyalkyl, hydroxypolyalkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonylalkyl, alkanoyl, aralkanoyl, aroyl, alkylsulfonyl or arylsulfonyl, for example the radicals stated in U.S. Pat. No. 3,998,802;

R14 is C1 -C8 -alkanoylamino or is benzoylamino which is unsubstituted or monosubstituted or disubstituted by hydroxyl, chlorine, methyl, methoxy, acetylamino, nitro or amino;

R15 is phenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl, dibromophenyl, methoxyphenyl, methylphenyl or dimethylphenyl;

R16 is COOCH3, COOC2 H5, phenyl, the radicals stated for R15, NHCOCH3, NHCOC2 H5, NHCOC3 H7, NHCOC6 H5, NHCOC6 H4 Cl, NHCOC6 H3 Cl2, NHCOC6 H4 Br, NHCOC6 H4 OCH3, NHCONH2, NHCONHC6 H5 or NHCOCONHC6 H5 ;

Other examples of suitable coupling components are 4-hydroxycoumarin, 2-acetonylbenzothiazole, 2-cyanomethylbenzpothiazole, 2-cyanomethylbenzimidazole, 2-cyanomethyl-4-hydroxyquinazoline, 2-hydroxyquinoxaline, 2-carbamylbenzimidazole, 2-acetonylbenzimidazole, 2-phenyl-4-amino-6-hydroxypyrimidine, 4-carbamyl-2,6-dihydroxypyrimidine, 2,4dihydroxypyrimido[1,2-a]benzimidazole, 4-amino-2-hydroxypyrimido[1,2-a]benzimidazole, 2H-pyrimido[2,1-b]benzothiazole-2,4-(3H)-dione, 1,4-(bisacetoacetamino)benzene and 4,'-bis-(acetoacetamino)-3,3'-dimethyldiphenyl.

Of particular importance are compounds of the formula Ia ##STR7## where K3 and K4 independently of one another are each a radical of a coupling component of the acetoacetarylide, pyrazolone, quinolone, pyrimidine, isoquinolone or pyrazolo[5,1-b]quinazolone series or of 2-naphthol and in particular a radical of the pyridine or 2-naphthol-3-carboxylic acid arylamide series, and the phenylene radicals A may be monosubstituted or polysubstituted by chlorine, bromine or nitro, the substituents being identical or different in the case of polysubstitution.

R1 is preferably NHC6 H5 which is unsubstituted or monosubstituted or polysubstituted by chlorine, bromine, methyl, methoxy, ethoxy, nitro, cyano, acetamino, carbamyl or sulfamyl, the substituents being identical or different in the case of polysubstitution, or is preferably ##STR8## R2 is preferably phenyl which is unsubstituted or monosubstituted or polysubstituted by chlorine, bromine, methyl, methoxy, ethoxy, nitro, cyano, acetamino, carbamyl or sulfamyl, the substituents being identical or different in the case of polysubstitution,

R3 is preferably hydrogen, methyl, C1 -C4 -alkoxycarbonyl, carbamyl, C1 -C4 -alkylaminocarbonyl or the radicals preferred for R2,

R4 is preferably hydrogen or the radicals preferred for R2,

R5 is preferably hydrogen or C1 -C8 -alkyl,

R6 is preferably hydrogen, methyl, hydroxyl or amino,

R7 is preferably hydrogen, cyano, carbamyl, acetyl or benzoyl,

R8 and R13 independently of one another are each preferably hydrogen, alkyl, alkenyl, cycloalkyl, benzyl or a radical R2,

R9, R10 and R11 independently of one another are each preferably hydrogen, alkyl, cycloalkyl, benzyl or a radical R2, and R10 and R11 together with the nitrogen may furthermore form a 5-membered or 6-membered ring,

R12 and R17 independently of one another are each preferably oxygen, imino or cyanoimino,

R14 is preferably a radical R8 or acylamino,

R15 is preferably hydrogen or a radical R2 and

R16 is preferably methyl or a radical R2.

The compounds of the formula (I) can be prepared by reacting a bisdiazonium compound of an amine of the formula (II) ##STR9## with coupling components HK1 and HK2, where HK1 and HK2 may be identical or different.

The coupling products (I) are as a rule pigments. They are not always obtained in the optimum physical form for the intended use. However, they may be converted to a suitable pigmentary form by a conventional method, such as milling, in the presence or absence of salts or liquids, or heating in aqueous suspension at a suitable pH or in a solvent.

Another possible method of improving the performance characteristics of the pigments is the known procedure of coating the pigments with compounds which preferably have a similar structure. For the preparation of the coating agent, it is generally advantageous to use the same diazo component and to vary the coupling component. In this case, a mixture of coupling components can be used from the outset for the pigment preparation, the coupling component which leads to the coating agent being added in appropriately small amounts, or the coating agent is synthesized separately and added to the pigmentat a later stage.

For the preparation of printing inks using pigments of the formula (I), it may be advantageous to improve the distribution properties of the pigments in the printing ink by prior coating with resins. Coating may be effected simultaneously with coupling, after coupling or after conditioning.

Some of the pigments of the formula (I) possess good color strength, fastness to overcoating and fastness to migration and are therefore suitable for the preparation of printing inks and surface coatings and for coloring plastics.

The Examples which follow illustrate the preparation and use of compounds of the formula (I). In the Examples, parts and percentages are by weight, unless stated otherwise.

Below, the radical ##STR10## is abbreviated to DIAP<, and substituted radicals are named correspondingly, eg. (5,5'-dibromo DIAP)<.

Examples EXAMPLE 1

32.4 parts of dianthranilic acid piperazide in 330 parts of water and 170 parts of ice are stirred, 70 parts by volume of concentrated hydrochloric acid are added and diazotization is carried out at room temperature with 64 parts by volume of 23% strength aqueous sodium nitrite solution. After 3 hours, the excess nitrite is destroyed with amidosulfonic acid. The diazotized compound is then gradually added, at 0 C., to a solution of 53.6 parts of N-(2,5-dimethoxy-4-chlorophenyl)-acetoacetamide in 600 parts of water, the said amide initially being dissolved under alkaline conditions and the solution then being brought to pH 6 with hydrochloric acid. Coupling is completed at room temperature at pH 6, and the pigment is filtered off under suction and washed with hot water. Thereafter, it is stirred in fresh water, stirred for 4 hours at pH 10 and 98 C., filtered off under suction, washed and dried. 80 parts of a yellow pigment are obtained, the compound being of the formula ##STR11##

EXAMPLE 2

16.2 parts of dianthranilic acid piperazide in 200 parts of water are stirred, 60 parts by volume of concentrated hydrochloric acid are added dropwise and diazotization is effected at 5 C. with 64 parts by volume of 23% strength aqueous sodium nitrite solution. Stirring is continued at room temperature until a clear solution is formed, the excess nitrite is destroyed with amidosulfonic acid, the solution is filtered, cooled to 0 C. and buffered at pH 2.5 with sodium acetate, and the coupling component prepared as described below is run in. 50 parts of 2-hydroxynaphthalene-3-carboxylic acid N-phenylamide and 1.4 parts of 2-naphthol are dissolved in 50 parts of N-methylpyrrolidone, 32 parts of 50 percent strengthsodium hydroxide solution and 500 parts of water at 45 C., and the solution is cooled to room temperature. Coupling is completed at 20 C. and the product is filtered off under suction and washed with water. The filter cake is stirred in water and brought to pH 10 with sodium carbonate, and 200 parts of a 10 percent strength aqueous rosin solution which has been rendered alkaline with sodium hydroxide are added. The mixture is stirred for 4 hours at 95 C., brought back to pH 7, kept at 95 C. for a further 2 hours and cooled to 60 C., and the product is filtered off under suction, washed with water and dried at 60 C. 103 g of red pigment are obtained. The principal component is of the formula ##STR12## and the important secondary component is of the formula ##STR13##

EXAMPLE 3

101 parts of dianthranilic acid piperazide in 600 parts of water are stirred with the addition of 0.6 part of the sodium salt of an alkylnaphthalenesulfonic acid. 180 parts by volume of concentrated hydrochloric acid are added, after which stirring is continued for 1 hour. Diazotization is carried out at 5 C. with 180 parts by volume of a 23 percent strength aqueous solution of sodium nitrite. The temperature is allowed to increase to 20 C. in the course of 3 hours, excess nitrite is destroyed with amidosulfonic acid, and the solution is run into a suspension of the coupling component, the suspension being prepared as described below. 104.4 parts of 3-methyl-1-phenylpyrazol-5-one are dissolved in 600 parts of water and 360 parts of 2N sodium hydroxide solution, the solution is cooled to 0 C. and precipitated with 1:1 glacial acetic acid/water, and 208 parts of a 10 percent strength rosin solution are then added, the said solution having been rendered alkaline with sodium hydroxide. Coupling is completed by bringing the pH to 4 by adding sodium acetate. The mixture is stirred overnight, after which it is filtered under suction and the residue is washed. The moist press cake is introduced into water, brought to pH 1.2 with dilute hydrochloric acid and stirred for 4 hours at 95 C. Filtration under suction, washing and drying in an oven at 60 C. give 272 parts of yellow pigment. The compound is of the formula ##STR14##

EXAMPLE 4

32.4 parts of dianthranilic acid piperazide in 120 parts of water are stirred with the addition of 0.2 part of the sodium salt of alkylnaphthalenesulfonic acid. After the addition of 50 parts by volume of 30 percent strength hydrochloric acid, a solution is formed for a short time and the hydrochloride is then precipitated. The mixture is cooled to 5 C., after which diazotization is carried out using 60 parts by volume of 23 percent strength aqueous sodium nitrite solution. Stirring is continued for 2 hours at room temperature, and the excess nitrite is destroyed with amidosulfonic acid. After filtration to effect clarification, a mixture of a solution of 30 parts of 3-cyano-2,6-dihydroxy-4-methylpyridine in 100 parts by volume of 2N sodium hydroxide solution, 600 parts by volume of water and 650 parts of a 10 percent strength aqueous alkaline rosin solution is added dropwise. Thereafter, the mixture is heated at 90 C. for three hours and the product is filtered off under suction, washed neutral with water and dried at 60 C. to give 123 g of a yellow pigment. The compound is of the formula ##STR15##

EXAMPLE 5

44 parts of dianthranilic acid piperazide in 150 parts of water are stirred with the addition of 0.2 part of the sodium salt of an alkylnaphthalenesulfonic acid. 150 parts by volume of concentrated hydrochloric acid are added, after which stirring is continued for one hour. The mixture is cooled to 5 C. and diazotization is then carried out using 81 parts by volume of a 23 percent strength aqueous sodium nitrite solution. Excess nitrite is destroyed with amidosulfonic acid. 63 parts of 3-cyano-N-hexyl-6-hydroxy-4-methylpyrid-2-one are dissolved in 750 parts of water with the addition of NaOH at 50 C., and the solution is filtered. This solution is cooled to room temperature, after which the diazonium salt solution is run in, the latter solution having been clarified by filtration. Stirring is continued for one hour at 50 C. and for one hour at 95 C., after which the product is filtered off under suction, washed neutral with hot water and dried at 70 C. to give 109 parts of a yellow pigment. The compound is of the formula ##STR16##

EXAMPLE 6

32.4 parts of dianthranilic acid piperazide in 120 parts of water are stirred with the addition of 0.2 part of the sodium salt of an alkylnaphthalenesulfonic acid. 75 parts by volume of concentrated hydrochloric acid are added, after which stirring is continued for one hour. Diazotization is carried out at room temperature with 64 parts by volume of a 23 percent strength aqueous sodium nitrite solution, after which excess nitrite is destroyed with amidosulfonic acid. 39 parts of N-butyl-3-cyano-6-hydroxy-4-methylpyrid-2-one and 1.6 parts of 3-cyano-2,6-dihydroxy-4-methylpyridine are dissolved in 300 parts of water with 8 parts of NaOH, and the solution is mixed with 152 parts of a 10 percent strength aqueous rosin solution. The diazonium salt solution is filtered into the mixture. Stirring is continued for half an hour, after which the pH is brought to 1.2, the mixture is stirred for 4 hours at 95 C. and the product is then filtered off under suction, washed and dried at 40 C. to give 92.5 parts of a yellow pigment. The principal component is of the formula ##STR17## and the important secondary component is of the formula ##STR18##

EXAMPLE 7

172 parts of piperazine and 968 parts of 5-bromoisatoic anhydride in 2000 parts of dioxane are stirred under reflux for 3 hours. The suspension is diluted with 500 parts of ethanol and filtered under suction, the filter cake is washed with ethanol and then with water and is then stirred in 2800 parts of 10 percent strength hydrochloric acid for 4 hours at 95 C. The product is filtered off under suction, washed neutral and dried at 70 C. Yield: 631 parts, bromine content: 31.6%.

53.6 parts of the resulting diazo component are boiled up in 500 parts of glacial acetic acid, the mixture is cooled to 5 C. and 58 parts of nitrosylsulfuric acid are then added dropwise. Stirring is continued for 3 hours at room temperature, the mixture is precipitated on ice, excess nitrite is destroyed by adding urea, and the mixture is run into the coupling component, which is prepared as prepared below. 15 parts of 2,6-dihydroxy-3-cyano-4-methylpyridine are dissolved in water which has been rendered alkaline, and precipitated at 0 C. by adding dilute hydrochloric acid. Coupling is carried out at 0 C. and pH 6. The pigment is filtered off under suction, washed, stirred in water at pH 10 for 4 hours at 98 C., filtered off under suction, washed neutral and dried to give 80 parts of a yellow pigment. The compound is of the formula ##STR19##

The other colorants may also be prepared by processes similar to those described:

______________________________________ ##STR20##Example No.     R1               Color______________________________________8         OCH3             red9         OC2 H5      red10      ##STR21##            red11      ##STR22##            red12      ##STR23##            red13      ##STR24##            red14      ##STR25##            red15      ##STR26##            red16      ##STR27##            red17      ##STR28##            red18      ##STR29##            red19      ##STR30##            red20      ##STR31##            red21      ##STR32##            red22      ##STR33##            red23      ##STR34##            red24      ##STR35##            red25      ##STR36##            red26      ##STR37##            red27      ##STR38##            red28      ##STR39##            red29      ##STR40##            red30      ##STR41##            red31      ##STR42##            red32      ##STR43##            red33      ##STR44##            red34      ##STR45##            red35      ##STR46##            red36      ##STR47##            red37      ##STR48##            red38      ##STR49##            red______________________________________

______________________________________ ##STR50##Example No.     R2               Color______________________________________39      ##STR51##            yellow40      ##STR52##            yellow41      ##STR53##            yellow42      ##STR54##            yellow43      ##STR55##            yellow44      ##STR56##            yellow45      ##STR57##            yellow46      ##STR58##            yellow47      ##STR59##            yellow48      ##STR60##            yellow49      ##STR61##            yellow50      ##STR62##            yellow51      ##STR63##            yellow52      ##STR64##            yellow53      ##STR65##            yellow54      ##STR66##            yellow55      ##STR67##            yellow56      ##STR68##            yellow57      ##STR69##            yellow58      ##STR70##            yellow______________________________________

______________________________________ ##STR71##Example No.      R3        R4                            Color______________________________________59         NH2       H      yellow60         CH3       H      yellow61         C6 H5                     H      yellow62         C6 H5                     C6 H5                            yellow63         CONH2     C6 H5                            yellow64         COOCH3    C6 H5                            yellow65         COOC2 H5                     C6 H5                            yellow______________________________________

______________________________________ ##STR72##Example No.  R4        Color______________________________________66         ##STR73##     yellow67         ##STR74##     yellow68         ##STR75##     yellow69         ##STR76##     yellow70         ##STR77##     yellow71         ##STR78##     yellow72         ##STR79##     yellow73         ##STR80##     yellow74         ##STR81##     yellow75         ##STR82##     yellow76         ##STR83##     yellow77         ##STR84##     yellow78         ##STR85##     yellow79         ##STR86##     yellow80         ##STR87##     yellow81         ##STR88##     yellow82         ##STR89##     yellow______________________________________

______________________________________ ##STR90##Example No.    R          Color______________________________________83             H          yellow84             4-Cl       yellow85             2,4-Cl2                     yellow86             4-CH3 yellow87             4-NO2 yellow88             4-OCH3                     yellow89           ##STR91## yellow90           ##STR92## yellow91             2,5-(OCH3)2                     yellow92             2,5-Cl2                     yellow______________________________________

______________________________________ ##STR93##Example No.     R5   Color______________________________________93              H         yellow94              CH3  yellow95              C2 H5                     yellow96              C3 H7 (n)                     yellow97            ##STR94##                     yellow98              C4 H9 (n)                     yellow______________________________________

______________________________________ ##STR95##Example No.  R8         Color______________________________________ 99          CH3        yellow100          C2 H5 yellow101          C3 H7 (n)                        yellow102         ##STR96##      yellow103          C4 H9 (n)                        yellow104          CH2 CH(CH3)2                        yellow105          CH(CH3)C2 H5                        yellow106          C5 H11 (n)                        yellow107          CH(C2 H5)2                        yellow108          C2 H4 CH(CH3)2                        yellow109          CH2 C(CH3)3                        yellow110         ##STR97##      yellow111          C(CH3)2 C2 H5                        yellow112         ##STR98##      yellow113         ##STR99##      yellow114         ##STR100##     yellow115         ##STR101##     yellow116         ##STR102##     yellow117         ##STR103##     yellow118          CH2C 6 H5                        yellow119          CH(CH3)C6 H5                        yellow120          CH(CH3)C2 H4 C6 H5                        yellow121          C6 H5 yellow122          C8 H17 (n)                        yellow123          C10 H21                        yellow124          C12 H25                        yellow125          C14 H29                        yellow126          C16 H33                        yellow127          C18 H37                        yellow128          C20 H41                        yellow129          C7 H15                        yellow130          C13 H17                        yellow        (isomer mixture)131          C9 H19                        yellow        (isomer mixture)132          C18 H35                        yellow133          C16 H31                        yellow134          C2 H4 OH                        yellow135          C2 H4 OCH3                        yellow136          C2 H4 OC2 H5                        yellow137          C3 H6 OH                        yellow138          C3 H6 OC2 H4 OH                        yellow139          CH2 CH(CH3)OH                        yellow140          C3 H6 OC2 H5                        yellow141          CH(C2 H5)CH2 OH                        yellow142          CH(CH3)CH2 OH                        yellow143          C3 H6 OCH3                        yellow144          C3 H6 OC9 H19 (iso)                        yellow145          CH2 C(CH3)2 CH2 OH                        yellow______________________________________

______________________________________ ##STR104##Example No.    R6  R7  R8    Color______________________________________146      CH3 CONH2                      H          yellow147      CH3 CONH2                      CH3   yellow148      CH3 CONH2                      C2 H5                                 yellow149      CH3 CONH2                      C3 H7 (n)                                 yellow150      CH3 CONH2                       ##STR105##                                 yellow151      CH3 CONH2                      C4 H9 (n)                                 yellow152      CH3 CONH2                       ##STR106##                                 yellow153      CH3 CONH2                       ##STR107##                                 yellow154      CH3 CONH2                      C5 H11 (n)                                 yellow155      CH3 CONH2                       ##STR108##                                 yellow156      CH3 CONH2                      C6 H13 (n)                                 yellow157      CH3 CONH2                      C8 H17 (n)                                 yellow158      CH3 CONH2                       ##STR109##                                 yellow159      CH3 H        H          yellow160      CH3 H        CH3   yellow161      CH3 H        C2 H5                                 yellow162      CH3 H        C3 H7 (n)                                 yellow163      CH3 H                       ##STR110##                                 yellow164      CH3 H        C4 H9 (n)                                 yellow165      CH3 H        C6 H13                                 yellow166      CH3 COCH3                      H          yellow167      CH3 COCH3                      CH3   yellow168      CH3 COCH3                      C2 H5                                 yellow169      CH3 COCH3                      C3 H7 (n)                                 yellow170      CH3 COCH3                       ##STR111##                                 yellow171      CH.sub. 3             COCH3                      C4 H9 (n)                                 yellow172      CH3 COCH3                      C6 H13                                 yellow173      CONH2             H        H          yellow174      OH       CN       H          yellow175      OH       CONH2                      H          yellow176      H        CN       H          yellow177      H        CN       CH3   yellow178      H        CN       C2 H5                                 yellow179      H        CN       C3 H7                                 yellow180      H        CN                       ##STR112##                                 yellow181      H        CN       C4 H9                                 yellow182      H        COCH3                      H          yellow183      H        COCH3                      CH3   yellow184      H        COCH3                      C2 H5                                 yellow185      H        COCH3                      C3 H7                                 yellow186      H        COCH3                       ##STR113##                                 yellow187      H        COCH3                      C4 H9                                 yellow188      H        CONH2                      H          yellow189      H        CONH2                      CH3   yellow190      H        CONH2                      C2 H5                                 yellow191      H        CONH2                      C3 H7                                 yellow192      H        CONH2                       ##STR114##                                 yellow193      H        CONH2                      C4 H9                                 yellow______________________________________

______________________________________ ##STR115##Example No.  X          Y        Color______________________________________194          HO         NH2 yellow195          HO         NHCH3                            yellow196          NH2   NH2 orange197          NHCH3 NHCH3                            orange198          NH2   NHCH3                            orange199          NHC2 H5                   NHC2 H5                            orange200          NH2   NHC2 H5                            orange201          NHC6 H5                   NHC6 H5                            orange202          NH2   NHC6 H5                            orange______________________________________

______________________________________ ##STR116##Example No.    R8 R12                   R13  R17                                   Color______________________________________203      H       O      H         O     yellow204      H       NH     H         O     yellow205      H       NH     H         NH    yellow206      H       NH     H         NCN   yellow207      H       O      H         NH    yellow208      H       O      CH3  O     yellow209      H       O      C2 H5                             O     yellow210      CH3            O      CH3  O     yellow211      CH3            O      C6 H5                             O     yellow212      C6 H5            O      C6 H5                             O     yellow213      H       O      C6 H5                             O     yellow214      CH3            O      CH3  NH    yellow215      H       O                    ##STR117##                             O     yellow216      H       O                    ##STR118##                             O     yellow______________________________________

______________________________________ ##STR119##Example No.     K1 H             Color______________________________________217      ##STR120##           red218      ##STR121##           yellow219      ##STR122##           yellow220      ##STR123##           yellow221      ##STR124##           yellow222      ##STR125##           yellow223      ##STR126##           yellow224      ##STR127##           yellow______________________________________

______________________________________ ##STR128##Example No.   R14     Color______________________________________225           H            yellow226           CH3     yellow227           C2 H5                      yellow228           C3 H7                      yellow229          ##STR129##  yellow230           C4 H9                      yellow231           NHC6 H5                      yellow232          ##STR130##  yellow233          ##STR131##  yellow______________________________________

______________________________________ ##STR132##Example No.   A           R16                            Color______________________________________234             7-Cl      CH3                            yellow235             7-Br      CH3                            yellow236           5,7-Cl2                     CH3                            yellow237             7-Cl, 5-Br                     CH3                            yellow238           5,7-Br2                     CH3                            yellow239             5-Cl      CH3                            yellow240             7-Br, 5-Cl                     CH3                            yellow241             8-Cl      CH3                            yellow242             7-Cl      C6 H5                            yellow243             7-Br      C6 H5                            yellow244             5-Cl      C6 H5                            yellow245           5,7-Cl2                     C6 H5                            yellow246           5,7-Br2                     C6 H5                            yellow247             8-Cl      C6 H5                            yellow248           H           CH3                            yellow249           H           C6 H5                            yellow______________________________________

______________________________________ ##STR133##Example No.     A         Color______________________________________250               5-Cl    yellow251               5-Br    yellow252             3,5-Cl2                     yellow253             3,5-Br    yellow254               3-Cl, 5-Br                     yellow255               3-Br, 5-Cl                     yellow______________________________________

______________________________________ ##STR134##Example No.      A           R8   Color______________________________________256          5-Cl      H         yellow257          5-Cl      CH3  yellow258          5-Cl      C2 H5                            yellow259          5-Cl      C3 H7                            yellow260          5-Cl                   ##STR135##                            yellow261          5-Cl      C4 H9                            yellow262          5-Br      CH3  yellow263          5-Br      C2 H5                            yellow264          5-Br      C3 H7                            yellow265          5-Br                   ##STR136##                            yellow266          5-Br      C4 H9                            yellow267          5-NO2                  H         yellow268          5-NO2                  CH3  yellow269          5-NO2                  C2 H5                            yellow270          5-NO2                  C3 H7                            yellow271          5-NO2                   ##STR137##                            yellow272          5-NO2                  C4 H9                            yellow273        3,5-Br2                  H         yellow274        3,5-Br2                  CH3  yellow275        3,5-Br2                  C2 H5                            yellow276        3,5-Br2                  C3 H7                            yellow277        3,5-Br2                   ##STR138##                            yellow278        3,5-Br2                  C4 H9                            yellow279        3,5-Cl2                  H         yellow280        3,5-Cl2                  CH3  yellow281        3,5-Cl2                  C2 H5                            yellow282        3,5-Cl2                  C3 H7                            yellow283        3,5-Cl2                   ##STR139##                            yellow284        3,5-Cl2                  C4 H9                            yellow285          3-Cl, 5-Br                  H         yellow286          3-Cl, 5-Br                  CH3  yellow287          3-Cl, 5-Br                  C2 H5                            yellow288          3-Cl, 5-Br                  C3 H7                            yellow289          3-Cl, 5-Br                   ##STR140##                            yellow290          3-Cl, 5-Br                  C4 H9                            yellow291          3-Br, 5-Cl                  H         yellow292          3-Br, 5-Cl                  CH3  yellow293          3-Br, 5-Cl                  C2 H5                            yellow294          3-Br, 5-Cl                  C3 H7                            yellow295          3-Br, 5-Cl                   ##STR141##                            yellow296          3-Br, 5-Cl                  C4 H9                            yellow297          6-Cl      H         yellow298          6-Cl      CH3  yellow299          6-Cl      C2 H5                            yellow300          6-Cl      C3 H7                            yellow301          6-Cl                   ##STR142##                            yellow302          6-Cl      C4 H9                            yellow______________________________________
EXAMPLE 303

162 parts of dianthranilic acid piperazide in 500 parts of water are stirred for a few hours with the addition of 0.5 part of a sodium alkylnaphthalenesulfonate. 275 ml of concentrated HCl are added, after which stirring is continued for 1/2 hour, ice is then added and diazotization is effected with 310 parts by volume of 23 percent strength aqueous sodium nitrite solution at from 0 to 5 C. After 11/2 hours, excess nitrite is destroyed with amidosulfonic acid and the solution is filtered.

41.4 parts of 3-cyano-6-hydroxy-1,4-dimethylpyrid-2-one are dissolved in a mixture of 100 parts of 2N sodium hydroxide solution and 600 parts of water with heating. 500 parts of a 10 percent strength aqueous rosin solution which has been rendered alkaline with sodium hydroxide are added at room temperature, and a solution of 2.9 parts of 3-cyano-6-hydroxy-4-methyl-1-(γ-trimethylammoniumpropyl)pyrid-2-one in 10 parts of glacial acetic acid is added dropwise. The diazonium salt solution is run into 85% of this suspension, while stirring thoroughly, and the mixture is titrated with the remaining 15% of the coupling component in the course of 1/2 hour until a small excess of diazo component is present. After 10 minutes, the pH is brought to 12 with 50 percent strength aqueous sodium hydroxide solution, stirring is continued for 5 minutes and the mixture is acidified with 30 parts of formic acid. The pH is then brought to 9 with sodium hydroxide solution and the mixture is stirred for 4 hours at 98 C. The pH is then brought to 5 with dilute hydrochloric acid, the mixture is cooled to 50 C. and the product is filtered off under suction, washed salt-free with water and dried at 50 C. to give 117 parts of a yellow pigment. The principal component is of the formula ##STR143## and the secondary components are of the formulae ##STR144##

The secondary coupling components stated in the table below can be used in a similar manner in the preparation of the pigments, also in combination with other principal coupling components. However, it is also possible to prepare the pure colorants DIAP→(secondary coupling component 1, secondary coupling component 2) and to add them before or after the principal coupling reaction which leads to the pigment.

______________________________________ ##STR145##Example No. R                 Color______________________________________304         C2 H4 N(CH3)2                         yellow305         C2 H4 N(C2 H5)2                         yellow306        ##STR146##       yellow307         C2 H4 N(C4 H9)2                         yellow308        ##STR147##       yellow309         C3 H6 N(CH3)2                         yellow310         C3 H6 N(C2 H5)2                         yellow311         C3 H6 N(C3 H7)2                         yellow312         C3 H6 N(CH(CH3)2)2                         yellow313         C3 H6 N(C4 H9)2                         yellow314        ##STR148##       yellow315        ##STR149##       yellow316        ##STR150##       yellow317        ##STR151##       yellow318        ##STR152##       yellow319        ##STR153##       yellow320         C3 H6 NHC12 H25                         yellow321         C3 H6 NHkokos                         yellow       (C8, C10, C12, C12, C16,                         yellow18)322         C3 H6 NHTalgfett                         yellow       (C14, C16, C18)323         C3 H6 NHOleyl                         yellow       (C14, C16, C18)324        ##STR154##       yellow325        ##STR155##       yellow326        ##STR156##       yellow327        ##STR157##       yellow328        ##STR158##______________________________________
EXAMPLES OF USE

(a) Surface coating

10 parts of the colorant obtained as described in Example 20 and 95 parts of a baking finish mixture containing 70% of coconut alkyd resin (60% strength solution in xylene) and 30% of melamine resin (roughly 55% strength solution in butanol/xylene) are milled in an attrition mill. After application and baking for 30 minutes at 120 C., red full-shade coatings possessing good depth and lightfastness are obtained. If titanium dioxide is added, red white reductions are produced.

If the colorants described in Examples 1-302 are used, some of the coatings obtained have good depth.

(b) Plastic (soft PVC)

0.05 part of a colorant obtained as described in Example 99 and 50 parts of a mixture of 65 parts of PVC powder, 36 parts of di-ethylhexyl phthalate and 2 parts of dibutyltin bis-(hexylthioglycolate) are homogenized on a roll mill at 150-160 C. for about 8 minutes, milled to give hides, and polished on a calender. Yellow sheets having good lightfastness and fastness to plasticizers are obtained. If titanium oxide is added during incorporation, yellow reductions of good depth are obtained.

If the pigment dyes obtained as described in Examples 1-302 are used, similar colorations are obtained.

(c) Printing ink

8 parts of the pigment dye obtained as described in Example 1, 40 parts of a rosin modified with phenol/formaldehyde, and from 55 to 65 parts of toluene are mixed thoroughly in a dispersing unit. A yellow toluene-based gravure printing ink is obtained. The prints obtained with this ink possess a good depth.

If the colorants of Examples 2-302 are used, similar results are obtained.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US4051123 *Aug 21, 1975Sep 27, 1977Ciba-Geigy AgSulfonic-acid-group containing disazo dyestuffs
DE2539162A1 *Sep 3, 1975Mar 17, 1977Basf AgAcid disazo dyes with good wet and light fastness - for dyeing of leather, paper and polyamides
JPS6094476A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4975118 *Jan 27, 1989Dec 4, 1990Basf AktiengesellschaftRecording fluid containing phenyl azo naphthalene dyes for the ink jet process
US6923855 *Aug 1, 2003Aug 2, 2005Fuji Photo Film Co., Ltd.Ink, ink-jet-recording method and bis-azo compound
US7732581 *Mar 25, 2009Jun 8, 2010Xerox CorporationColorant compounds
US7833685 *Nov 16, 2010Canon Kabushiki KaishaColoring compound and yellow toner containing the coloring compound
US20040129172 *Aug 1, 2003Jul 8, 2004Fuji Photo Film Co., Ltd.Ink, ink-jet-recording method and bis-azo compound
US20080220358 *May 13, 2008Sep 11, 2008Canon Kabushiki KaishaColoring compound and yellow toner containing the coloring compound
US20090182152 *Jul 16, 2009Banning Jeffrey HColorant Compounds
Classifications
U.S. Classification534/740, 534/728, 534/757, 534/605, 534/756, 534/649, 534/DIG.1, 534/745, 534/774, 534/797, 534/741, 534/764, 534/742, 534/772, 534/752, 534/573, 534/762, 106/31.77, 534/604, 534/650, 106/496, 534/603, 534/763, 106/498, 534/DIG.2, 534/773, 534/759
International ClassificationC09D11/037, C08K5/3462, C09D7/12, C08K5/3442, C09B35/28, C08K5/34
Cooperative ClassificationY10S534/02, Y10S534/01, C08K5/3462, C09B35/28, C09D11/037
European ClassificationC09D11/037, C09B35/28, C08K5/3462
Legal Events
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Owner name: BASF AKTIENGESELLSCHAFT, 6700 LUDWIGSHAFEN, RHEINL
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Owner name: BASF AKTIENGESELLSCHAFT,GERMANY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:COLBERG, HORST;HAHN, ERWIN;REEL/FRAME:004865/0943
Effective date: 19860922
Feb 3, 1992FPAYFee payment
Year of fee payment: 4
Mar 17, 1992REMIMaintenance fee reminder mailed
Mar 26, 1996REMIMaintenance fee reminder mailed
Aug 18, 1996LAPSLapse for failure to pay maintenance fees
Oct 29, 1996FPExpired due to failure to pay maintenance fee
Effective date: 19960821